Fabric printing



Patented June 10, 1941 Maurice Belioc, Paris, Nobel Francalse,

No Drawing.

Paris, stock company oi Fran Application June 30, 1937, Serial France,designer to Societe Seine, France, a jointce No. 151,321. In France July31, 19 38 a owns,- (or ill-68) The present invention. relates to aprocess of printing on fabrics? and to the fabrics obtained by applyingsaid process.

It is known to fix aqueous solutions or suspensions of dyes and ofpigments on fabrics by means of printing machines or of engraved blocksor of frames permitting the printing known as screen printing. Theaqueous solutions and suspensions used have in general gums, dextrine,

mucilages and various materials added to them whichgive them theviscosity necessary for the printing operation, the dyes or pigments arefixed on the fabric and finally the latter is washed to eliminate thewater-soluble thickeners.

The process which has just been described'has serious drawbacks:necessity of effecting a fixing operation and a washing operation afterthe printing, which are costly operations and which" lfurthermore mayalter the fabric, difficulties of over-dyeing a printed fabric, owing tothe fact that the printed parts are subjected to the overdyeing inxthesame manner as the non-printed parts, etc. 7

One of the objects of the present invention consists in having foundthat it is possibleto replace the aqueous solutions hitherto used forprinting by machine, or by means of ablock or by the screen process, bycolloidal solutions, in organic solvents, of cellulose esters or ofsynthetic resins or mixtures 'of same. By means of said colloidalsolutionsin organic solvents, impressions can be applied to fabrics, forexample with printing machines provided with known intaglio engravedcylinders, which impressions have, without a subsequent operation, theflexibility. the colours, the mechanical strength, the .fastness towashing of the impressions obtained with the known processes, when theoperations of fixing and of washing are completed.

Another object. of the invention consists in pro .viding a colloidalsolution or dispersion in which the colloidal material, the plasticizerand the solvent are selected to give properties making it possible toemploy the solution in the ordinary fabric printing processes.-

Previously known colloidal solutions have been unsuccessful for twoprincipal reasons: First, the rate of drying was not satisfactory,either too fast or too slow; Second, thesurface tension of the solutionswas too high so that difliculty was experienced in obtaining completeremoval of the solution from the printing surface, particularly from thedeep points of the surface. This second difficulty also caused troublein screen printing for the solution tended to form threads whichstreaked the printed surface and marred the efiect. v

The present invention, therefore,aims to produce a colloidal organicsolution for use in these application by the printing machine. After theprocesses and which has physical properties approximating those of thepreviously used aqueous solutions but which has theadvantages-attributable to the colloidal substance employed.

Amongst the cellulose esters nitrocellulose and acetylcellulose will beparticularly mentioned and amongst the synthetic resins the condensationproducts of polyvinyl alcohol with one or a plurality of aldehydes.

The choice of the solvents used for making the colloidal solutions usedaccording to the invention is of great importance. Such solvents shouldhave a fairly slow rate of evaporation, preferably approximating tothatof water. It has been found in the second place that it is oftenadvantageous to use water-soluble solvents; glycols, monochlorhydrins ofglycols, glycol esters, esters of glycol ethers, ethyl lactate, etc.

This selection of water-soluble solvents is a purely empirical test ofdesirability because it is not intended to use water in the compositionsbut the.

water-soluble solvents have, in general, been found best adapted byreason of their physical characteristics. The application of suchsolvents enables: I g

a. The filling of the engraved parts of the cylinder to be eife'ctedwithout a film forming on the non-engraved parts.

I). The drying of fected in the drying chambers or on" the heatedcylinders of the printing machines.

c. The colloidal solutions to be preserved during a normal time in thetank of .the printing machine, or in the work shop.

After being applied by the machine and-dried,

the impressions are perfectly adherent to the fibers and the printedfabric can be washed with- ,out special precautions as though theimpressions were effected by the known processes.

The two following examples give compositions which give excellentresults for efiecting the impressions according to the invention,without limiting it in any way.

In the above example, ethyl alcohol is used only to reduce the hazard ofhandling nitrocellulose in the dry state. Theethyl alcohol is merely anadditional solvent in the example and may be dispensed with or its placetaken by an additional amount of one of the other solvents. In thecomposition set out above the constituthe printed pieces to be efentshave approximately the following propor# tion:

a Per cent Nitrocellulose 20 Total plastifler 32 Total solven 48Depending on the plasticity desired for the resulting printed film theamount of plastifier may be varied. In like manner, the amount ofsolvent employed may be varied to change the viscosity and density ofthe solution.

Example I] Grammes Polyvinyl aceto-formal prepared according to theindications of my application Serial No.

748,263, dated the 13th of October, 1934-..- 300 Methyl phthalate(plastifier) 74 Butyl phthalate (plastifier) '74 Ethylparatoluenesulfamide (plastifier) 147 i Ethyl glycol acetate (solvent)300 Glycol monochlorhydrin (solvent) 400 Butyl glycol (solvent) 300 Inthe above example, the constituents have, the following approximaterelation:

Per cent Polyvinyl aceto-formal 18 Total plastifler 18 Total solv n 64solutions attack the metallic powders to a considerable extent, 'or atleast substantially alter their hue.

Moreover, it has been found that nitrocellulose colloidal solutions suchas those described in Example I, very quickly gelify whenbrought" intocontact with bronze powder.

For effecting metallicand, in particular, bronze impressions accordingto the invention, the composition of Example II gives very satisfactoryresults, or the following composition may also be used, without being inany way limitative'.

Example III Grammes Polyvinyl aceto-formal prepared according to myapplication Serial No. 748,263, dated the 13th of October, 1934 300over-printing of the parts protected by said solu- 'tions. In this casethe-necessary products are i zation.

Methyl phthalate (plastifier) .a 74 Butyl phthalate (plastifler) 74Ethylparatoluolsulfamide (plastifler) 147 Ethyl glycol (solvent) 300Xylene (solvent) 300 Ethyl lactate (solvent) 200 Ethyl glycol acetate(solvent); 200

Thesam e relative proportions exist here be tween the polyvinyla'ceto-formal and the total plastifier and total solvent as in Example11 above.

A suitable quantity, for example 200 grammes, of bronze powder is addedto this colloidal solution, and no substantial thickening effect isproduced thereby, so that the composition can be used industriallywithout danger of gelification.

The suspension thus obtained can be used for printing by machine or bymeans of a block, or by the screen process. It remains very stable withage, in particular it has no tendency to gelify, and its tendency toturn green decreases with the purity of the solvents.

Another point of the present invention consists in'having found that theapplication of the above described colloidal solutions, effected underthe normal conditions of use of the printing machines or the intaglioengraved cylinders, renders the fibres impregnated with said colloidalsolutions impervious to water while preserving their flexibility.

This operation consequently makes it possible to effect the most variedsubsequent treatments of the printed fabrics. Amongst such treatmentswill be cited:

a. The dyeing of the non-printed parts.

b. The physical and chemical treatments of the non-printed parts such asthe mercerizing" or the immunisation of cotton or of fibres of'regenerated cellulose by complete immersion, of the printed fabrics insuitable aqueous solutions.

c. The carbonizing of the parts which are not protected by the colloidalsolutions and the resist applied to the fabrics by the known means.

The following examples will enable the second object of the presentinvention to be better understood.

Example 1 A crepe de chine made of natural silk is first V printed, bythe means described, with a colloidal solution according to theinvention.

Dyeing is effected, to obtain a navy blue with:

Naphthylamine 5 BCL avy blue A cotton veil is first printed by the meansdescribed then padded in a bath of concentrated sulphuric acid (between55 and 62 Beaum) at 10 C. This impregnation lasts a few seconds and isfollowed by a very abundantrinsing effected in width. It is well knownthat concentrated sulphuric acid acts, on cellulose and renders itrelatively transparent or very translucid (.par-chmentization).Consequently, in the present'instanc, the printed parts are not alteredby. the acid treatmentwhereas the nonprinted parts undergo the usualparchmentizing effect. n

The fabric is then mercerized, rinsed, acidified, rinsed 'and 'tenteredaccording. to the known methods. The printed parts remain intact fromthe actions both of the acid and of the merc'eri- Example 3 A fabriccomposed of a backing of natural silk (warp and weft) and of a secondreinforcing warp sateen weave made of rayon is first printed the rayonparts 'tions of the invention remain intact.

by the means described. It is again printed with a suitably thickenedsolution of alumina. chloride or of alumina sulphate. The dry fabric iscarbonized according to the known processes and printed with thecolloidal solu- The invention is not limited to the specific disclosure,but it is to be limited only by the scope of the following claims.

What is claimed is:

1. In a fabric printing process, the step of printing on the fabric witha composition containing polyvinyl iiceto-formal approximately 18%.plastiflers totaling approximately 18%, and solvents totalingapproximately 64%.

taining polyvinyl aceto-formal; plastifiers including methyl phthalate,butyl phthalate, ethyl paratoluenesulphamide; and solvents includingethyl glycol acetate, glycol monochlorhydrin,

butyl glycol. c l

MAURICE BELLOC.

